N-{8 o-aryl-thionoalkanephosphonyl{9 iminoformic acid alkyl esters

ABSTRACT

O-aryl-thionoalkanephosphonic acid ester-formamidines or iminoethers of the formula   in which R is lower alkyl, R&#39;&#39; is lower alkoxy, mono-lower alkyl-amino or di-lower-amino, and Ar is optionally halogen-substituted phenyl, which possess insecticidal, acaricidal and nematocidal properties.

United States Patent [1 1 Hoffmann et al.

[451 Nov. 25, 1975 [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany Filed: July 16, 1974 Applv No: 489,795

Related U.S. Application Data [62 Division of Ser. No. 431.831 Jan. 9. 1974.

[30] Foreign Application Priority Data Jun. 27. 1973 Germany 2304062 [52] US. Cl 260/950; 260/944; 260/945;

260/968; 424/220 [51] Int. Cl. C07F 9/24; AOlN 9/36 [58] Field of Search 260/950 [56] References Cited UNITED STATES PATENTS 3.767.736 10/1973 Burke 260/950 Primary Examiner-Anton H. Sutto Attorney. Agent. or FirmBurgess. Dmklage & Sprung 57 ABSTRACT O-aryl-thionoalkanephosphonic acid esterformamidines or imino-ethers of the formula in which R is lower alkyl, R is lower alkoxy, mono-lower alkyl-amino or di-lower-amino, and Ar is optionally halogen-substituted phenyl, which possess insecticidal, acaricidal and nematocidal properties.

6 Claims, N0 Drawings N-[O-ARYL-THIONOALKANEPHOSPHONYL- ]IMINOFORMIC ACID ALKYL ESTERS This is a division of application Ser. No. 431,833, filed Jan. 9, 1974.

The present invention relates to and has for its objects the provision of particular new O-aryl-thionoalkanephosphonic acid ester-formamidines or iminoethers which possess insecticidal, acaricidal or nematocidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g., insects, acarids, and nematodes, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

The present invention relates to certain new O-arylthionoalkanephosphonic acid esterimide derivatives, to a process for their preparation and to their use as insecticides, acaricides or nematocides.

It is known from Belgian Patent Specification No.-

766,191 that O-aryl-thionoalkanephosphonic acid ester-amides, such as O-(3-chloro- (Compound A) or 2,4- (Compound B) or 2,6-dichloro- (Compound C) and 2,4,5-trichlorophenyl)-thionoethanephosphonic acid ester-amide (Compound D), display insecticidal, acaricidal and nematocidal properties.

The present invention provides O-aryl-thionoalkanephosphonic acid ester-formamidines of imino-ethers of the general formula ArO S in which R is lower alkyl,

R is lower alkoxy, mono-lower alkyl-amino or dilower-alkyl-amino, and

Ar is optionally halogen-substituted phenyl.

Preferably, R is straight-chain or branched alkyl with l to 4, especially 1 to 3, carbon atoms; Ar is phenyl which is monosubstituted or polysubstituted by chlorine, and R is alkoxy or mono-alkylamine or dialkylamino with l to 4, especially 1 to 3, carbon atoms per alkoxy or alkyl moiety.

Surprisingly, the O-aryl-thionoalkanephosphonic acid ester-formamidines and imino-ethers of the formula (1), according to the invention, display a substantially better insecticidal, especially soil-insecticidal, acaricidal and nematocidal action than previously known compounds of analogous structure and of the same type of action. The compounds according to the invention thus represent a genuine enrichment of the art.

The invention also provides a process for the production of an O-aryl-thionoalkanephosphonic acid esterformamidine or imino-ether of the formula (I) in which a. an O-aryl-thionoalkanephosphonic acid esteramide of the general formula is reacted with a dialkoxy compound ofthe general formula AlkO CHR' (lll) AlkO b. a phosphorylated imino-formic acid alkyl ester of the general formula ArO S is reacted with a primary or secondary alkylamine of the general formula c a o 2 5 \CH-OC a P-NH 2 c a 0 c 11 2 I (Ha) (II a) -2cuon a (Ila) (IIIb) 01 (VII) (VIII) R, R and R" in the formulae (1V) and (V) preferably denote straight-chain or branched alkyl with l to 4, especially 1 to 3, carbon atoms.

The O-aryl-thionoalkanephosphonic acid esteramides (11) to be used as starting compounds have already been described in the literature and are obtainable according to customary processes, for example according to Belgian Patent Specification No. 766,191; equally, the orthoformic acid alkyl ester derivatives (111) can be prepared according to known methods.

lndividually, the following may be mentioned as examples of such compounds: O-(2-, 3- and 4-chloro-, 2,4- and 2,6dichloro-, 2,4,5- and 2,4,6-trichloroor 2,3,4,5,6-pentachlorophenyl) methanephosphonic acid ester-amide and the corresponding -ethane-, npropaneand -iso-propanederivatives, and also orthoformic acid trimethyl, ethyl, n-propyl and iso-propyl esters.

Some of the N-alkylor N,l\l-dialkyl-formamidedialkylacetals also to be used as starting compounds are new but they can be prepared according to processes which are in themselves known, e.g., Chemische Berichte, 101 (1968), page 46. The following may be mentioned individually as'examples of acetals to be used in the present process: N (methyl-, ethyl-, n-propyl-, isopropyl)- or N. l l(dimethyl-, diethy1, di-n-propyl-, di-isopropyl)-formamidedimethylor -diethylacetal.

The alkylamines (V) required as starting compounds in process variant (b) are known from the literature and can also be prepared on an industrial scale. The following may be mentioned individually as examples thereof: methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, isopropylamine and di-iso-propylamine.

Examples of phosphorylated iminoformic acid alkyl' esters (1V) include: l l-[2-, 3 and 4-chloro-, 2,4- and 2.6-dichloro-, 2,4,5- and 2,4,6-trichloroor 2,3,45,6- pentachlorophenyl)-thionomethaneor ethane, -npropaneand iso-propane-phosphoryll-iminoformic acid methyl esters and the corresponding ethyl esters and propyl esters.

The process of the invention can be carried out in the presence of a diluent. Practically all inert organic solvents can be employed for this purpose. These include in particular aliphatic and aromatic optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; ethers, for example diethyl ether, dibutyl ether and dioxane; ketones', for example acetone, methyl ethyl ketone, methyl isopropyl ltetone and methyl isobutyl ketone; and nitriles, for example acetonitrile and propionitrile.

in process variant (a), when an orthoformic acid alkyl ester is one of the reactants, the reaction can optionally be carried out in the presence of an acid catalyst, for example toluenesulfonic acid.

The reaction temperature can be varied over a wide range. In general, the reaction is carried out at about 60 to 200, preferably about 1 l to 180C, in process variant (a), and at about 0 to 150, preferably about 40 to 50C, in variant (b). The reaction is usually allowed to take place under normal pressure.

To carry out process variant (a), the two reactants are preferably brought together in the absence ofa solvent or diluent but optionally in the presence of an acid catalyst, the dialkoxyxcomponent (lll) inmost cases. being added in about to excess. The reaction mixture is then heated for between one and several hours to the indicated temperatures, at the same time and the mixture is stirred for between one and several 7 hours at the indicated temperatures and then worked up in the usual way.

Some of the new compounds are obtained in the form stituents by so-called slight distillation, that is to say. prolonged heating under reduced pressure to moderately elevated temperatures, and they can in this way index. Some of the compounds are obtained in a crystalline form of sharp melting point. i

As already mentioned, the O-aryl-thionoalkanephos phonic acid ester-imide derivatives according to the in-. vention are distinguished by an outstanding insecti-.

cidal, including soil-insecticidal, acaricidal and nematocidal activity. They couple a low phytotoxicity with a good action against both sucking and biting insects. I

For this reason, the compounds according to the in 3 0 vention can be employed successfully pesticides in plant protection and in the hygiene field and field of stored products. To the sucking insects there being, in the main, aphids (Aplzidae) such as the green peach aphid (Myzus persicae), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosip/mm padi), the pea aphid (Macrosip/mm pisi) and the potato aphid (Macrosip/ium solamfolii), the currant gall aphid (Cryplomyzus korschelti), the rosy apple aphid (Sappaphis nmli), the 4O mealy plum aphid (Hyaloptefus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiorus liederae) and the soft scale (Lecanium lzesperidum) as well as the grape mealybug (Pseuaucoccus maritimus); thrips (T/zysanoptera), such as Hereinarlzrips femomlis, and bugs, for example the beet bug (Piesnza quadrata), the red cotton bug (D \'sa'ercu.r.intermedius), the bed bug (Cimex lectularius), the assassin I I bug (Rliodnius prolixzls) and Chagas bug (Triatoma in- SOfestans) and, further, cicadas, such as Euscelis bilobatus and Nep/zorettix bipimctazus.

In the case of the biting insects, above all there should be mentioned butterfly caterpillarstLepidoptera) such as the diamond-back moth (Plutella maculi pemzis), the gypsy moth (Lymantria dispar), the browntail moth (Euproctis clirysorrhoea) and tent caterpillar (Malacosoma lzeuslria); further, the cabbage moth (Mamestm brassicae) and the cutworm (Agi'olis sagetum), the large white butterfly (Pieris brassicae), the small winter moth (Cheimarobia brumaza), the green oak tortrix moth (Tortrix viridana), the fall .armyworrn (Lap/zygma.frugiperda) and cotton worm (Pi'cdenia,

litum), the ermine moth (Hyponomeuta padella), the

Mediterranean flour moth (Epliestia ku/rniella) and I greater wax moth (Galleria mellonella). U

Also to be classed with the biting insects are beetles (Coleopzera), for example the granary weevil (Siroof oils which mostly cannot be distilled without decom position but which can be freed of the last volatile conbe purified. They are characterized by the refractive.

p/iilus granm'ius Calandra granaria), the Colorado beetle (Leptinorarlra decen lineqla), the dock beetle (Gastrophysa viridula), the mus'tard beetle'(P/zaed0n coclzleariae), the blossom beetle (Meligetlies aeneus), the raspberry beetle (Byzurustomentosus), the bean weevil (Bruchidius Acantlwscelides obtecms), the leather beetle (Dermestes frisc/ii), the khapra beetle (Trogoderma granarium),-the flour beetle (Tribolium casraneum), the northern corn billbug (Calandra or Sitopliilus Zeamais), the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle (Oryzaephilzis surinamensis), and also species living in the soil, for example wireworms (Agriores spec.) and larvae of the cockcha fer (Melolont/m melolontha); cockroaches, such as the German cockroach (Blattella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Leucopiiaea or Rlzyparobia mademe), oriental cockroach (Blarta orientalis), the giant cockroach (Blabems gigameus) and the black giant cockroach (Blaberus fuscus) as Well as Hensclioutedenia flexiritta;

further, ()rrlwptem, for example the house cricket (Achera demesrz'cus); termites such as the eastern subterranean termite (Reliculilermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius lzz'ger). I

The Diptera comprise essentially the flies, such as the vinegar fly (Drosop/zila melmzogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia cariicularis), the

black blow fly (P/zormia regina) and bluebottle fly (Cal lip/m erytlzrocepliala) as well as the stable fly (Stom0.\' \'s caicitmirs); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi).

With the mites (Acari) there are classed, in particular, the spider mites (Tetranycliidae) such as the twospotted spider mite (Tetraliyc/ius urticae) and the Euro pean red mite (Paratetranyclzus pilosus PGIIOH \'C]1US ulmi), gall mites, for example the blackcurrant gall mite (Erioplzyes ribi's) and tarsonemids, for examplethe broad mite (Hemitarsoiiemus laws) and the cyclamen case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier mite (Tarsonenms pallidus); finally ticks, such as the relapsing fever tick (Omit/rodents moubata).

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the active compounds are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e., plant compatible or herbicidally inert) pesticide diluents or extenders, i.e,, diluents, carriers or extenders of the type usable in conventional pesticide formuiations or compositions, e.g., conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in'the vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g., benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffms (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g, dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silica'tes, e.g. alkali silicates, etc,); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and- /or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as l'ignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides and nematocides, for fungicides, bactericides, rodenticides, herbicides, fertilizers, growthregulating agents, etc., if desired, or in form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes and granules, which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0001l0%, preferably 0.0ll%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which'comprises mixtures of a conventional dispersible carrier vehicle such as (l) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g., a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is 7 effective for the purpose in questions and which is generally between about 0.000l-95/(, and preferably 0.0l95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via every effective atomizing equipment, in finely divided form, egv average particle diameter of from 50-100 microns, or even less, i.e mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about to 1,000 g/hectare, preferably 40 to 600 g/hectare, are sufficient. in this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about to about 95% by weight of the active compound or even the 100% active substance alone, eg about 20-l007z by weight of the active compound,

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g., insects, acarids and nematodes, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (e) such nematodes, and (d) the corresponding habitat thereof, i.e., the locus to be protected, a correspondingly combative or toxic amount, i.e. an insecticidally, acaricidally, or nematocidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinklingpouring, fumigating, dressing, encrusting and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 The O-aryl-thionoalkanephosphonic acid esteramides to be used as starting compounds were prepared, for example, as follows:

97 g (0.3 mole) of O-(2,4,5-trichlorophenyl)-thionoethanephosphonic acid ester-chloride were added at 10 to 20C to a mixture of 60 ml of aqueous ammonia and 300 ml of acetonitrile, the reaction solution was stirred for one hour and evaporated, and the residue was taken up in methylene chloride. The organic phase was washed with water and dried, the solvent was distilled off and the residue was recrystallized from ligroin. 65 g (71% of theory) of O-(2,4,5-trichlorphenyl)- thionoethanephosphonic acid ester-amide of melting point 74C were obtained.

Table 1 Physical z operties Yield melting 5 of t Structure point c) theory) S. l g 7 CH a e HZN c1' cu 7, :P-O -c1 47 7Q H N CH3 3 t u r-o-c1 48-49 74 H N 2 3 1 0 as 75 H N EXAMPLE 2" C1 Cl 3 i -N=CH-OC H 0 c H /P 2 5 A mixture of 153 g (0.5 mole) of O-(2,4,5-trichl0rophenyl)-thionoethanephosphonic acid ester-amide and g of orthoformic acid ethyl ester was heated in the presence of approximately 0.5 g of p-toluenesulfonic acid for 1 hour at C, the resulting alkanol was distilled off and the reaction solution was suction-filtered.

After slight distillation of the filtrate, 174 g (97% of theory) of N[O-(2,4,5-trichlorophenylHhionoethane:

phosphonyll-iminoformic acid ethyl ester of refractive index H024: 1.5601 were obtained,

EXAMPLE 3 A mixture of 30 g (0.135 mole) of O-(3-chlorophenyl)-thionomethanephosphonic acid ester-amide and 30 g of N,N-dimethylformamide-dimethylacetal was heated for 2 hours under reflux. The resulting ethanol was then distilled off under reduced pressure, giv- 9 ing, as the residue, 36 g (97% of theory) of O-(3- chlorophenyl)-N-(N',N-dimethylaminomethylidene)- thionomethanephosphonic acid ester-imide of refractive index n,,'-*: 1.5900. The initially oily substance crystallized and then had a melting point of 90C.

EXAMPLE 4 EXAMPLE 5 The following compounds were prepared analogously to the method described in the above examples.

labial Physical Yield properties of theory Structure n c H O-CH=N (4) 1.5580 g S 01 25 sq g 1a 95 c 1r o-cn=n 1.5555

-(-5-) ca cl 25.

1.5660 c a o-ca=n 01 CH tag 84 1,6010 MI RE-01k (7) 5 '1' o. c1 74-76% 60 c -NH-CH=N t '0 'c1 0 ca -NH-CH=H/ 79 c 46 P-0--c1 102% 79 (cn n-cr1=n t x hlg 2 -('o l u'd l hg'sical Yield properties (A of theory) Structure 2 5\i; cl 49-51 C 72 H N-CH=N C1 0 n5 92 (c a N CH=N 1.5725

S CH 3 u 25 P-O CZHSMM/ Q n 94 EXAMPLE 6 Plutella test Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) were sprayed with the preparation of the active compound until dew moist and were then infested with caterpillars of the diamond-back moth (Plutella masculipennis).

After the specified periods of time, the degree of destruction was determined as a percentage: means that all the caterpillars were killed whereas 0% means that none of the caterpillarswere killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 3:

Table 3 (Plutella test) Active com- Table 3 (unli nucd (Plutella test) Active com- Degree of gggz zggg destruction r in after in y a a weight 3 aye Active compound 1 0.1 100 r on -1 o 0.01 95 3 0.001 85 N=G1-i-N(C H i 2a 100 100 3 Q 0.001 1.00

N=CH- 0 11 (6) s c .3 10o n 100 c n -a0 -01 00001 90 l 01 Xi=CH-NH-CH r p e 0.1 100 m 0,01 100 2 P 0 C1 0.001 100 mutationi EXAMPLE 7 Hyzus testtcontzic't action) 7 I Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl' polglycol ether I To produce a suitable preparation of ,active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which had been heavily infested with peach aphids (Myzus persicae) were sprayed with the preparation of the active compound until dripping wet. I v 1 After the specified periods of time, the degree of destruction was determined as a percentage: 100% means that all the aphids were killed whereas 0% means that none of the aphids were killed.

The active compounds, the concentrations of the ac tive compounds, the evaluation times and the results can be seen from the following Table 4:

Table (11y zus test) Table 4 (continued) (Myzus test) Active corn- Degree pound conof descen$ration 'trngtion in a by in Active compound weight after 1 dav (known) t" 2a, 95 MOB-( 0,0001 50 on -i -0 c1 I 3 l 0.01 99 I men-M0119 (001 95 Cl N-CH-N(C H C1 g=oH-N(GH EXAMPLE 8 Rhopalosiphum test (systemic action) soil without wetting the leaves of the oat plants. The active compound was taken up by the oat plants from the soil and thus reached the infested leaves.

After the specified periods of time, the degree of de- 7 struction was determined as a percentage: 100% means that all the aphids were killed whereas 0% means that none of the aphids were killed.

The active compounds, the concentrations of the ac- I tive compounds,'the evaluation times and the'results can be seen from the following Table 5:

gable 5 (Rhogalosiphum test) I Active com- Degree 01 pound condestruction centration in 9 after Active compound in by 4 1 days weight s e I C1 7 I! P O- l 0 z s o 14 XAMPLE 9 Tetranychus test (resistant) 13 Table 5 (continued) (iihogalosiphum test) Solvent: 3 parts by weight of acetone Active compound con- Degree of destruction ccnqration Active compound To produce a suitable preparation of active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate was 01 diluted with water to the desired concentration. NHZ

(known) Bean plants (Plzaseolus vulgaris), which had a height of approximately 30 cm, were sprayed with the preparation of the active compound until dripping wet.

These bean plants were heavily infested with the com-.

(known) mon or two-spotted spider mite (Tetranychus urticae) in all stages of development.

After the specified periods of time, the effectiveness of the preparation of active compound was determined (known) uction by counting the dead mites. The degree of destr thus obtained is expressed as a percentage:

0.1 100% means that all the spider mites were killed whereas 0% means that none of the spider mites were killed.

7; The active compounds, the concentrations of the active compounds, the evaluation times and the results 100 can be seen from the following Table 6:

Table 6 (Tetr chus test) Man ma-0H .0 O8 O0 0 O9 O2 1 1 l l l 10 1M 0 H. 00 \1 00 m 0 o 3 H C H l 0 4 C m m I m H H H w 4 w 4 c SuP N n N S N 3 n c w 5 O 5 5 5 008 O5 00 0 O9 00 N1 1 11 l 10 l l 100 1O 10 000 00 O0 w n I MI 2 I\ m 3 H5 5 H l 2 H C C C 2 C C Q a H H l a a a a c J we SuJ N SnJ N Snvn 3 3 H H C C w mm w 11 1 1 10 l 0o 2 o u 2 M \l 5 5 H H 1 c c 1 N C a o w 4 p" snvm 3 H H c c 0 5 6 6 ow O0 0 O4 11 1 1 1m 10 0o 00 \I 5 6 m 5 m H 2 2 c m W 1 H C n 0 c a w Sams t H H C C Table 6 (continued) (Tetranxchus test) Active com- Critical concentration test Test nematode: Meloidogyne incognita Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound was mixed with the stated amount of solvent, the stated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

The preparation of active compound was intimately mixed with soil which was heavily infested with the test nematodes. The concentration of the active compound in the preparation was of practically no importance; only the amount of active compound per unit volume of soil, which is given in ppm-(by weight) was decisive. The soil was filled into pots, lettuce was sown in and the pots were kept at a greenhouse temperature of 27C. After 4 weeks, the lettuce roots were examined for infestation with nematodes, and the degree of effectiveness of the active compound was determined as a percentage. The degree of effectiveness was 100% when infestation is completely avoided; it was 0% when the infestation was exactly the same as in the case of the control plants in untreated soil which had been infested in the same manner.

The active compound, the amounts applied and the results can be seen from the following Table 7:

Table 1 V (Meloidogxne :tnco'mitg test) Active compound Degree of, destruction in at an active compound concentration 7 1o 5 2.5 ppm fi o -c1 0 n -P 2 (known) T511101 (continued (Meloidome incoggitg teat Active compound Degree of destruction in at an active compound concentration of I 2O 1O 5 2.5 M b S O u c1 0 C H P\ (a) (known) S ll/ 0 C H -P i 1 (lmotm) S 100 CH -P H=Cl'i-lH i-CH cir -i 95- 3o NnCH-NH-CH on 2 100 9a 90 so i 3 1r-cu n S l CH 100 98 9o 50 3 N on N C2H5 It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing fromthe spirit r and scope of the present invention.

What is claimed is:

1. An O-aryl-thionoalkanephosphonic acid esterimide derivative of the formula compound is N-[O(2,4-dichlorophenyl)-thionomethanephosphonyll-iminoformic acid ethyl ester of the formula Cl S 3\ 3. The compound according to claim 1 wherein such compound is N-[O-(2,4,5-trichlorophenyl)-thionoethanephosphonyl]-iminoformic acid ethyl ester of the formula 4. The compound according toclaim 1 wherein such compound is N-[O-(2-chlorophenyl)-th ionomethanephosphonyH-iminoformic acid ethyl ester of the formula CH s 01 6. The compound according to claim 1 wherein such compound is N-[O-(4-chlorophenyl)-thionomethanephosphonyl]-iminoformic acid ethyl ester of the formula 

1. AN O-ARYL-THIONOALKENEPHOSPHONIC ACID ESTER-IMIDE DERIVATIVE OF THE FORMULA
 2. The compound according to claim 1 wherein such compound is N-(O-(2,4-dichlorophenyl)-thionomethanephosphonyl)-iminoformic acid ethyl ester of the formula
 3. The compound according to claim 1 wherein such compound is N-(O-(2,4,5-trichlorophenyl)-thionoethanephosphonyl)-iminoformic acid ethyl ester of the formula
 4. The compound according to claim 1 wherein such compound is N-(O-(2-chlorophenyl)-thionomethanephosphonyl)-iminoformic acid ethyl ester of the formula
 5. The compound according to claim 1 wherein such compound is N-(O-(3-chlorophenyl)-thionomethanephosphonyl)-iminoformic acid ethyl ester of the formula
 6. The compound according to claim 1 wherein such compound is N-(O-(4-chlorophenyl)-thionomethanephosphonyl)-iminoformic acid ethyl ester of the formula 